JPH032881B2 - - Google Patents
Info
- Publication number
- JPH032881B2 JPH032881B2 JP13372681A JP13372681A JPH032881B2 JP H032881 B2 JPH032881 B2 JP H032881B2 JP 13372681 A JP13372681 A JP 13372681A JP 13372681 A JP13372681 A JP 13372681A JP H032881 B2 JPH032881 B2 JP H032881B2
- Authority
- JP
- Japan
- Prior art keywords
- microcrystalline cellulose
- water
- etherification
- carboxymethylated
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 46
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 46
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 46
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006266 etherification reaction Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000013312 flour Nutrition 0.000 description 5
- 239000000546 pharmaceutical excipient Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 235000008429 bread Nutrition 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035807 sensation Effects 0.000 description 3
- 235000019615 sensations Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000287826 Gallus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000008278 cosmetic cream Substances 0.000 description 1
- 239000008271 cosmetic emulsion Substances 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229940124531 pharmaceutical excipient Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229920003124 powdered cellulose Polymers 0.000 description 1
- 235000019814 powdered cellulose Nutrition 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000014438 salad dressings Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000020183 skimmed milk Nutrition 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- -1 super-aids Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
本発明は微結晶セルロースの表面をカルボキシ
メチル化して得られるセルロース誘導体及びその
製法に関するものである。ここで云う微結晶セル
ロースとは、パルプ、リンター、木綿などのセル
ロース原料を酸加水分解に付し、非結晶領域を洗
滌、除去した後、磨砕、精製、乾燥して得られる
微粉末セルロースで、通常粒径100μ以下の粉体
である。微結晶セルロースは成形性、分散懸濁安
定性、チキソトロピー性、生理的無害性及び無味
無臭、無色性などの特徴のため種々の用途に利用
されている。即ち、医薬品賦形剤、過助剤、食
品添加剤、分散剤、粘度改良剤などに用いられて
いる。特に食品には低カロリー増量剤としての機
能も重視されるようになつて来ている。
しかしながら、微結晶セルロースだけではゾ
ル、ゲル、コロイドの乳化懸濁安定剤や増粘剤と
しては実用上充分でなく、水溶性高分子を併用す
る必要がある。また、微結晶セルロースは舌ざわ
りが悪いので、その添加量が制限されるか、ある
いは水溶性高分子との併用や水溶性高分子でコー
テイングした微結晶セルロースが用いられている
(特開昭53−72868、特開昭54−157875、特開昭55
−34006など)。これらの水溶性高分子との併用、
あるいはコーテイングしたものの使用でも味覚の
点では不充分か、粘度が上りすぎて流動性が失わ
れるなど利用面で難しいものである。
本発明は微結晶セルロースの表面層だけをカル
ボキシメチル化することにより、分散・懸濁安定
性を増大せしめる一方、微結晶セルロースに滑ら
かな舌ざわり性を賦与させ、食品添加物として好
適なものとすることができることを見出したこと
にある。微結晶セルロースの表面をカルボキシメ
チル化する方法及びその製品の繊維用糊剤への応
用が特公昭45−19438に示されている。該明細書
には水を媒体として水酸化ナトリウム水溶液で微
結晶セルロースを処理し、モノクロル酢酸水溶液
を加え、カルボキシメチル化微結晶セルロースを
得る方法が示されている。しかしながらこのよう
にして作製されたカルボキシメチル化微結晶セル
ロースは皮膜形成性、アルカリ可溶性などの性能
を有し、むしろカルボキシメチルセルロースに近
く、粉体流動性、崩壊性などの特性が失われ、賦
形剤などの用途には不適である。特公昭45−
19438は微結晶セルロースの表面を主にカルボキ
シメチル基を導入したものであるが、この方法で
はそれでも若干内部にまでエーテル化が浸透して
しまう。微結晶セルロースの特性をかえることな
くカルボキシメチルエーテル化するにはその反応
をごく表面層にのみ止める必要がある。
本発明者らは鋭意研究の結果、微結晶セルロー
スのごく表面層のみをカルボキシメチルエーテル
化する方法として、有機溶媒を反応媒法としたス
ラリー法を用い、しかも反応系内の水の量を極め
て制限された範囲で使用することにより目的とす
る微結晶セルロース誘導体を得ることに成功し
た。即ち、本発明は脂肪族アルコール/水混合溶
媒中にモノクロル酢酸を溶かし、次いで微結晶セ
ルロースを加えてスラリー化した後、水酸化ナト
リウムを添加してエーテル化する製法において、
混合溶媒中の水の濃度を5%以下で行うことによ
りアルセル化の際の膨潤と内部浸透を抑制しつつ
反応させ、且つエーテル化度が全体として0.05〜
0.8となるようにして得られる微結晶セルロース
カルボキシメチルエーテル及びその製法に関する
ものである。
本発明の微結晶セルロース誘導体は賦形剤、懸
濁安定剤、食品添加剤などの用途に使用すること
ができ、分散安定性、保形性、舌ざわりなどが原
料微結晶セルロースに比べて改良されたものであ
る。本発発明の微結晶セルロース誘導体の用途と
して好適なものは、例えば乾式打錠用賦形剤、ア
イスクリーム、マヨネーズ、サラダドレツシン
グ、パン、化粧用クリーム、化粧用乳液などであ
る。
以下に実施例をあげて本発明を説明するが、エ
ーテル化度、粉体としての平均粒径、流動性、水
に対する分散性は次の方法で試験し、数値化し
た。
1 エーテル化度(DS)
乾燥試料1gを精秤し、定量紙に包んで白金
ルツボ又は磁製ルツボ中に入れ、静かに加熱して
炭化した後、600℃を越えない温度で灰化し、冷
却後500mlビーカーにルツボを移し、水約250mlを
加え、更にN/10H2SO450mlを正確に加え30分
間煮沸する。これを冷却し、フエノールフタレイ
ン指示薬を加え、過剰の酸をN/10NaOH溶液に
て滴定する。同様に空試験を行ない、次式により
エーテル化度を求める。
A=(B−S)×F/乾燥試料g−アルカリ度 注1
エーテル化度(モル)=162×A/10000−80A
B:空試験に要したN/10NaOHの使用量
(ml)
S:実試験 〃
F:N/10NaOH溶液の力価
注)アルカリ度の求め方
乾燥試料約1gを精秤し、水約200mlを加えて溶
解する。これにN/10H2SO4、5mlを正確に加
えて10分間煮沸し、冷却した後フエノールフタレ
イン指示薬を加えN/10NaOHにて滴定する。
アルカリ度=5F′−N/10NaOH(ml)数×F/乾燥試
料g
F:N/10NaOH溶液の力価
F′:N/10H2SO4〃
2 平均粒径
乾式篩分法によるメデイアン径
3 流動性指数
パウダーテスター((株)細川粉体工学研究所製)
を使つてゆるみ見掛比重、固め見掛比重、安息
角、スパチユラ角、粒度分布を測定し、総合的に
指数化したもの、数値が大きい程流動性が良いこ
とになる。
(参考資料)
「パウダーテスターよる粉粒体の流動特性試験と
その応用」
横山藤平(株)細川粉体工学研究所
昭和51年6月3日、日本粉体工業協会主催
粉体工業講座(第23回)
4 水への分散性
乾燥試料30gをとり、水270mlを加え、高速度
(毎分8000回転以上)で5分間混ぜた後、その100
mlを100mlのメスシリンダーに入れ、6時間放置
後の上澄液の厚みを測定し、分散層の厚みを100
として換算したもの。従つて数値が小さい程分散
性が良いことになる。
微結晶セルロースの製造例
市販の亜硫酸木材パルプを細断し、0.5%塩酸
溶液中で125℃、1時間加水分解して得られた酸
不溶解残査を中和・洗滌し、磨砕し、噴霧乾燥し
た。乾燥物を35メツシユの篩で粗大物を除き、平
均粒径65μ、重合度200、結晶化度75の白色の微
結晶セルロースAを得た。得られた微結晶セルロ
ースAの赤外線吸収スペクトラムを第1図に示
す。
比較例 1
製造例で得られた微結晶セルロースAをイソプ
ロパノール/水混合溶媒を用い、均一なエーテル
化反応生成物が得られる公知の条件下でカルボキ
シメチル化した。
微結晶セルロースA100gをイソプロパノール
(IPA)1180gと水100gとNaOH40gの混合溶液系
に入れ、室温で90分間撹拌した。このスラリー系
に50%のモノクロル酢酸(MCA)のIPA溶液60g
を入れ室温で30分間撹拌した後、60℃に昇温し、
2時間継続させた。反応終了後固形分を75%メタ
ノール水溶液で洗滌し、エタノールで置換後乾燥
した。得られた白色微粉末をBとする。Bの赤外
線吸収スペクトラムを第2図に示す。
実施例 1〜5及び比較例 2
製造例で得られた微結晶セルロースAを、
IPA/水混合溶媒を用い、且つ水の量が少い条件
下でカルボキシメチル化した。
イソプロパノール(IPA)1180gに所定量の水
とモノクロル酢酸(MCA)を溶かし、次いで
A100gを入れ、スラリー状態にした。このスラリ
ー系に所定量の水酸化ナトリウム(NaOH)を顆
粒状で少しづつ撹拌状態で加えて後、昇温し反応
させた。反応終了後固形分を75%メタノール水溶
液で洗滌し、エタノールで置換後乾燥した。
反応条件を表−1に、エーテル化度及びその他
の物性測定値を表−2に示す。又、実施例−2、
4の製品の赤外吸収スペクトラムをそれぞれ第3
図、第4図に示す。
The present invention relates to a cellulose derivative obtained by carboxymethylating the surface of microcrystalline cellulose and a method for producing the same. The microcrystalline cellulose referred to here is finely powdered cellulose obtained by subjecting cellulose raw materials such as pulp, linter, and cotton to acid hydrolysis, washing and removing amorphous regions, and then grinding, refining, and drying. , usually a powder with a particle size of 100μ or less. Microcrystalline cellulose is used for various purposes due to its characteristics such as moldability, dispersion/suspension stability, thixotropy, physiological harmlessness, tasteless, odorless, and colorless properties. That is, it is used in pharmaceutical excipients, super-aids, food additives, dispersants, viscosity modifiers, and the like. In particular, the function of foods as low-calorie bulking agents is becoming more important. However, microcrystalline cellulose alone is not practically sufficient as an emulsion suspension stabilizer or thickener for sols, gels, and colloids, and a water-soluble polymer must be used in combination. In addition, since microcrystalline cellulose has a unpleasant texture, the amount added is limited, or microcrystalline cellulose is used in combination with a water-soluble polymer or coated with a water-soluble polymer (Japanese Patent Application Laid-Open No. 1983-1999-1). 72868, 1978-157875, 1978 Japanese Patent Publication
−34006 etc.). Combined use with these water-soluble polymers,
Alternatively, even if a coated product is used, it is difficult to use because the taste is insufficient or the viscosity increases too much and fluidity is lost. The present invention increases dispersion/suspension stability by carboxymethylating only the surface layer of microcrystalline cellulose, while imparting smooth texture to the microcrystalline cellulose, making it suitable as a food additive. The goal is to discover what can be done. A method of carboxymethylating the surface of microcrystalline cellulose and the application of the product to a sizing agent for textiles are disclosed in Japanese Patent Publication No. 19438/1983. The specification describes a method of obtaining carboxymethylated microcrystalline cellulose by treating microcrystalline cellulose with an aqueous sodium hydroxide solution using water as a medium and adding an aqueous monochloroacetic acid solution. However, the carboxymethylated microcrystalline cellulose produced in this way has properties such as film-forming properties and alkali solubility, and is rather similar to carboxymethylcellulose. It is unsuitable for applications such as agents. Special Public Service 1977-
19438 mainly introduces carboxymethyl groups onto the surface of microcrystalline cellulose, but with this method, etherification still penetrates slightly into the inside. In order to convert microcrystalline cellulose into carboxymethyl ether without changing its properties, it is necessary to limit the reaction to only the very surface layer. As a result of extensive research, the present inventors found that a slurry method using an organic solvent as a reaction medium was used to carboxymethyl etherify only the very surface layer of microcrystalline cellulose, and the amount of water in the reaction system was extremely small. By using it within a limited range, we succeeded in obtaining the desired microcrystalline cellulose derivative. That is, the present invention is a manufacturing method in which monochloroacetic acid is dissolved in an aliphatic alcohol/water mixed solvent, then microcrystalline cellulose is added to form a slurry, and sodium hydroxide is added to etherify the mixture.
By keeping the concentration of water in the mixed solvent at 5% or less, the reaction can be carried out while suppressing swelling and internal penetration during alcelization, and the degree of etherification can be maintained at 0.05 to 0.05 as a whole.
0.8, and a method for producing the same. The microcrystalline cellulose derivative of the present invention can be used as an excipient, suspension stabilizer, food additive, etc., and has improved dispersion stability, shape retention, texture, etc. compared to the raw material microcrystalline cellulose. It is something that Suitable applications for the microcrystalline cellulose derivative of the present invention include, for example, excipients for dry tableting, ice cream, mayonnaise, salad dressings, bread, cosmetic creams, and cosmetic emulsions. The present invention will be explained below with reference to Examples. The degree of etherification, average particle size as a powder, fluidity, and dispersibility in water were tested and quantified by the following methods. 1 Degree of etherification (DS) Accurately weigh 1 g of the dry sample, wrap it in quantitative paper, place it in a platinum crucible or porcelain crucible, heat it gently to carbonize it, then ash it at a temperature not exceeding 600℃, and then cool it. Transfer the crucible to a 500 ml beaker, add about 250 ml of water, then add exactly 50 ml of N/10H 2 SO 4 and boil for 30 minutes. It is cooled, phenolphthalein indicator is added and excess acid is titrated with N/10N a OH solution. Perform a blank test in the same manner, and determine the degree of etherification using the following formula. A = (B-S) x F/dry sample g-alkalinity Note 1 Degree of etherification (mol) = 162 x A/10000-80A B: N/10N required for blank test Amount of a OH used (ml) S: Actual test 〃 F: Potency of N/10N a OH solution Note) How to determine alkalinity Accurately weigh approximately 1 g of the dry sample and dissolve it by adding approximately 200 ml of water. Accurately add 5 ml of N/10H 2 SO 4 and boil for 10 minutes. After cooling, add a phenolphthalein indicator and titrate with N/10N a OH. Alkalinity = 5F'-N/10N a Number of OH (ml) x F/g dry sample F: N/10N a Potency of OH solution F': N/10H 2 SO 4 〃 2 Average particle size Dry sieving method Median diameter 3 Flowability index Powder tester (manufactured by Hosokawa Powder Engineering Institute Co., Ltd.)
The loosened apparent specific gravity, hardened apparent specific gravity, angle of repose, angle of spatula, and particle size distribution are measured using the , and the values are comprehensively converted into an index. The larger the value, the better the fluidity. (Reference material) "Flow characteristic test of powder and granular material using powder tester and its application" Yokoyama Tohei Co., Ltd. Hosokawa Powder Technology Research Institute June 3, 1976, Powder Industry Lecture (No. 1) sponsored by the Japan Powder Industry Association 23 times) 4 Dispersibility in water Take 30 g of a dry sample, add 270 ml of water, mix at high speed (more than 8000 revolutions per minute) for 5 minutes, and then
ml into a 100 ml graduated cylinder, and after standing for 6 hours, measure the thickness of the supernatant liquid, and calculate the thickness of the dispersed layer by 100 ml.
Converted as . Therefore, the smaller the numerical value, the better the dispersibility. Production example of microcrystalline cellulose Commercially available sulfite wood pulp is shredded and hydrolyzed in a 0.5% hydrochloric acid solution at 125°C for 1 hour. The resulting acid-insoluble residue is neutralized and washed, and the resulting pulp is ground. Spray dried. The dried product was passed through a 35-mesh sieve to remove coarse materials, yielding white microcrystalline cellulose A having an average particle size of 65 μm, a degree of polymerization of 200, and a degree of crystallinity of 75. The infrared absorption spectrum of the obtained microcrystalline cellulose A is shown in FIG. Comparative Example 1 Microcrystalline cellulose A obtained in Production Example was carboxymethylated using an isopropanol/water mixed solvent under known conditions to obtain a uniform etherification reaction product. 100 g of microcrystalline cellulose A was placed in a mixed solution system of 1180 g of isopropanol (IPA), 100 g of water, and 40 g of NaOH , and the mixture was stirred at room temperature for 90 minutes. Add 60g of 50% monochloroacetic acid (MCA) to this slurry system in IPA.
After stirring at room temperature for 30 minutes, raise the temperature to 60℃,
It continued for 2 hours. After the reaction was completed, the solid content was washed with a 75% aqueous methanol solution, replaced with ethanol, and then dried. The obtained white fine powder is designated as B. The infrared absorption spectrum of B is shown in FIG. Examples 1 to 5 and Comparative Example 2 Microcrystalline cellulose A obtained in the production example,
Carboxymethylation was carried out using an IPA/water mixed solvent with a small amount of water. Dissolve the specified amount of water and monochloroacetic acid (MCA) in 1180g of isopropanol (IPA), then
Add 100g of A to make a slurry. A predetermined amount of sodium hydroxide (N a OH) was added little by little in the form of granules to this slurry system while stirring, and then the temperature was raised to cause a reaction. After the reaction was completed, the solid content was washed with a 75% aqueous methanol solution, replaced with ethanol, and then dried. The reaction conditions are shown in Table 1, and the degree of etherification and other physical property measurements are shown in Table 2. Moreover, Example-2,
The infrared absorption spectra of the 4 products are shown in the 3rd column.
As shown in Fig. 4.
【表】【table】
【表】【table】
【表】
比較例−3及び4
微結晶セルロースAを特公昭45−19438に示さ
れた水を溶媒とする方法によりカルボキシメチル
化した。即ち、同公報記載の実施例−1における
市販微結晶セルロースにかえてAを用いた他は同
様にしてカルボキシメチル化微結晶セルロースを
得た。即ちA600gに45%水酸化ナトリウム水溶液
を1.1加え、5℃に冷却しながら30分間撹拌し
た後、46%モノクロル酢酸水溶液を0.55及び1.20
と添加量をかえ60℃で1時間反応させた。反応
が進むに従い正成物の表面が溶媒に溶けた状態に
なつた。特にモノクロル酢酸1.20添加の方は糊
状になつた。冷却後塩酸中和して遊離とし、メタ
ノール添加による沈澱、遠心分離、水酸化ナトリ
ウム添加によるナトリウム塩再生、メタノール沈
澱、乾燥を行つたが、その過程で粒子同志の溶着
が認められ、原料微結晶セルロースとは異つた粒
子形状のものとなつた。
生成物のエーテル化度及び透明度の測定結果を
表−3に示す。透明度は次の方法で試験し、数値
化した。
透明度
高さ250m/m、内径25m/m、厚さ2m/mの
ガラス円筒の底に厚さ2m/mの良質ガラス板を
密着させ、このガラス円筒を巾1m/m、間隔
1m/mの15本の平行線を黒く書いた白紙の上に
置く。このガルス円筒の中に試料の1%懸濁水溶
液を入れて上部から透視するとき、線が判別でき
なくなる1%懸濁水溶液の高さを透明度とする。
試料が水に良く溶ける程透明度は大きくなる。[Table] Comparative Examples 3 and 4 Microcrystalline cellulose A was carboxymethylated by the method described in Japanese Patent Publication No. 45-19438 using water as a solvent. That is, carboxymethylated microcrystalline cellulose was obtained in the same manner as in Example 1 described in the same publication, except that A was used instead of commercially available microcrystalline cellulose. That is, 45% sodium hydroxide aqueous solution was added to 600 g of A, and after stirring for 30 minutes while cooling to 5°C, 46% monochloroacetic acid aqueous solution was added at 0.55 and 1.20 g.
The amount of addition was changed and the reaction was carried out at 60°C for 1 hour. As the reaction progressed, the surface of the product became dissolved in the solvent. In particular, when 1.20% of monochloroacetic acid was added, the mixture became pasty. After cooling, it was neutralized with hydrochloric acid to release it, precipitated by adding methanol, centrifuged, sodium salt regenerated by adding sodium hydroxide, precipitated with methanol, and dried, but during the process, welding of particles was observed, and the raw material microcrystals. The particle shape was different from that of cellulose. Table 3 shows the results of measuring the degree of etherification and transparency of the product. Transparency was tested and quantified by the following method. Transparency A high-quality glass plate with a thickness of 2m/m is tightly attached to the bottom of a glass cylinder with a height of 250m/m, an inner diameter of 25m/m, and a thickness of 2m/m.
Place 15 parallel lines of 1m/m on a blank sheet of black paper. When a 1% aqueous suspension of a sample is placed in this Gallus cylinder and viewed from above, the height of the 1% aqueous suspension at which lines cannot be distinguished is defined as transparency. The better the sample dissolves in water, the greater the transparency.
【表】【table】
【表】
応用例 1
製造例で得たA及び実施例−1,2で得た表面
カルボキシメチル化微結晶セルロースを用いて医
薬錠剤打錠試験を行つた。これらを賦形剤とし、
アスコルビン酸49%、賦形剤50%、ステアリン酸
マグネシウム0.5%、タルク0.5%の混合物を同一
条件で直接打錠した結果を表−4に示す。[Table] Application Example 1 A pharmaceutical tablet compression test was conducted using A obtained in Production Example and the surface carboxymethylated microcrystalline cellulose obtained in Examples 1 and 2. These are used as excipients,
Table 4 shows the results of direct compression of a mixture of 49% ascorbic acid, 50% excipients, 0.5% magnesium stearate, and 0.5% talc under the same conditions.
【表】
但し、硬度・磨損度の測定法は次の通りである。
硬度
モンサント硬度計を使用して20個の錠剤の各々
の硬度を測定し、その平均値を採用した。
磨損度
直径30cmの単翼式錠剤磨損度試験機を使つて試
料を50錠仕込み、25回転/分で10分間衝撃を与え
た。衝撃後に錠剤を取り出して破損分離した粉お
よび小粒子を篩別除去して重量を測定し、重量減
をもとの重量に対する百分率で表示した。
応用例 2
製造例で得たA及び実施例−2で得た表面カル
ボキシメチル化微結晶セルロースを用いて乳化安
定性試験を行つた。
水200g、砂糖10g、脱脂粉乳15gの混合スラリ
ーを2セツト(No.1とNo.2)準備し、No.1に
A20g、No.2に表面カルボキシメチル化微結晶セ
ルロース20gを加え、ホモミキサーを使つて同一
条件で乳化した。乳化後の観察結果を表−5に記
載した。[Table] However, the method for measuring hardness and abrasion is as follows. Hardness The hardness of each of the 20 tablets was measured using a Monsanto hardness meter, and the average value was taken. Abrasiveness Using a single-blade tablet abrasion tester with a diameter of 30 cm, 50 tablets of the sample were loaded and subjected to impact at 25 revolutions/min for 10 minutes. After impact, the tablets were taken out, broken and separated powder and small particles were removed by sieving, and the weight was measured, and the weight loss was expressed as a percentage of the original weight. Application Example 2 An emulsion stability test was conducted using A obtained in Production Example and the surface carboxymethylated microcrystalline cellulose obtained in Example-2. Prepare two sets (No. 1 and No. 2) of mixed slurry of 200 g of water, 10 g of sugar, and 15 g of skim milk powder.
20 g of surface carboxymethylated microcrystalline cellulose was added to 20 g of A, No. 2, and emulsified under the same conditions using a homomixer. The observation results after emulsification are listed in Table-5.
【表】
応用例 3
微結晶セルロースA及び実施例−2で得た表面
カルボキシメチル化微結晶セルロースを舌の上に
乗せた感触を味わうテストを10人のパネラーで実
施したところ、10人全員共微結晶セルロースAは
多少ザラザラした感触及び異物感を与えるのに対
して、表面カルボキシメチル化微結晶セルロース
の方はなめらかな感触で全く異物感を与えないと
解答した。
応用例 4
次にこれらの微結晶セルロース及び誘導体を添
加したパンを作成した。
前種
小麦粉(強力粉) 1400g
イースト 40g
イーストフード 4g
水 700g
を〓ね、26〜27℃で2時間保持して1次発酵さ
せた。
次に上記前種に下記処方の〓粉を加え本〓し
た。
本〓
小麦粉(薄力粉) 300g
添加物(微結晶セルロースなど) 300g
砂糖 100g
食塩 50g
マーガリン 100g
ドライミルク 40g
水 600g
〓和後所定のパンローフを得る大きさに分割し、
27℃で10分間熟成、次いでベーキング用型に入れ
て37℃で40分間2次発酵させた。
次いでオーブン中約230℃で45〜70分間焼き上
るまで加熱した。
添加物は次のものである。
No.1 無添加(薄力粉を合計600g使用)
No.2 製造例のA
No.3 市販の微結晶セルロース(アビセルRC
−N−81)
No.4 実施例−2の表面カルボキシメチル化微
結晶セルロース
焼き上りの外見と試食結果を表−6に示す。[Table] Application example 3 When 10 panelists conducted a test to taste the sensation of placing microcrystalline cellulose A and the surface carboxymethylated microcrystalline cellulose obtained in Example-2 on the tongue, all 10 panelists Microcrystalline cellulose A gave a somewhat rough feel and a foreign body sensation, whereas surface carboxymethylated microcrystalline cellulose had a smooth feel and did not give a foreign body sensation at all. Application Example 4 Next, bread to which these microcrystalline cellulose and derivatives were added was prepared. Preliminary flour (strong flour) 1400g, yeast 40g, yeast food 4g, water 700g were mixed and held at 26-27°C for 2 hours for primary fermentation. Next, the following powder was added to the above mixture and the mixture was prepared. Main flour (soft flour) 300g Additives (microcrystalline cellulose, etc.) 300g Sugar 100g Salt 50g Margarine 100g Dry milk 40g Water 600g After warming, divide into pieces that will make the desired bread loaf.
The mixture was aged at 27°C for 10 minutes, then placed in a baking mold and subjected to secondary fermentation at 37°C for 40 minutes. It was then heated in an oven at about 230°C for 45-70 minutes until baked. The additives are as follows. No. 1 No additives (600g of soft flour used in total) No. 2 Production example A No. 3 Commercially available microcrystalline cellulose (Avicel RC)
-N-81) No. 4 Surface carboxymethylated microcrystalline cellulose of Example-2 The baked appearance and tasting results are shown in Table-6.
【表】
○:良
△:やや劣る
×:劣る
[Table] ○: Good △: Slightly poor ×: Poor
図面は微結晶セルロース及び微結晶セルロース
のカルボキシメチル化物のKBr錠剤法で測定した
赤外吸収スペクトラムである。
第1図……微結晶セルロース、第2図……カル
ボキシメチル化物、第3図,第4図……表面カル
ボキシメチル化物。
The figure shows infrared absorption spectra of microcrystalline cellulose and carboxymethylated microcrystalline cellulose measured by the KB r tablet method. Figure 1: Microcrystalline cellulose; Figure 2: carboxymethylated product; Figures 3 and 4: surface carboxymethylated product.
Claims (1)
合溶媒中でナトリウム・カルボキシメチルエーテ
ル化するにあたり、水/脂肪族アルコールの重量
比が6/100〜2/100の範囲で、かつ水/グルコ
ースのモル比を3〜5の範囲で行い、エーテル化
剤としてモノクロル酢酸と固形水酸化ナトリウム
を用いることを特徴とする微結晶セルロースの粒
子表面をグルコース単位あたり0.05以上0.8以下
の置換度でナトリウム・カルボキシメチルエーテ
ル化した水不溶性で水分散性の微結晶セルロース
誘導体の製造方法。1 When sodium carboxymethyl etherification of microcrystalline cellulose is carried out in an aliphatic alcohol/water mixed solvent, the weight ratio of water/aliphatic alcohol is in the range of 6/100 to 2/100, and the molar ratio of water/glucose is 3 to 5, and using monochloroacetic acid and solid sodium hydroxide as etherification agents, the particle surface of microcrystalline cellulose is treated with sodium carboxymethyl ether at a substitution degree of 0.05 to 0.8 per glucose unit. A method for producing a water-insoluble and water-dispersible microcrystalline cellulose derivative.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13372681A JPS5834802A (en) | 1981-08-25 | 1981-08-25 | Microcrystalline cellulose derivative and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13372681A JPS5834802A (en) | 1981-08-25 | 1981-08-25 | Microcrystalline cellulose derivative and its production |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5834802A JPS5834802A (en) | 1983-03-01 |
JPH032881B2 true JPH032881B2 (en) | 1991-01-17 |
Family
ID=15111467
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13372681A Granted JPS5834802A (en) | 1981-08-25 | 1981-08-25 | Microcrystalline cellulose derivative and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5834802A (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6094401A (en) * | 1983-10-31 | 1985-05-27 | Asahi Chem Ind Co Ltd | Cellulose dervative having excellent liquid absorption characteristic, its production and structure containing the same |
JPH0673860B2 (en) * | 1985-07-16 | 1994-09-21 | パイオニア株式会社 | Fresnel lens manufacturing mold |
FR2784107B1 (en) * | 1998-09-15 | 2005-12-09 | Rhodia Chimie Sa | SURFACE MODIFIED CELLULOSE MICROFIBRILLES, THEIR PREPARATION PROCESS, AND THEIR USE |
US6602994B1 (en) * | 1999-02-10 | 2003-08-05 | Hercules Incorporated | Derivatized microfibrillar polysaccharide |
FR2800378A1 (en) * | 1999-11-03 | 2001-05-04 | Saint Louis Sucre Sa | Cellulose microfibers used in composites and paints, have hydroxyl groups substituted by ether groups localized at the surface and with a specified degree of surface substitution |
JP2008238115A (en) * | 2007-03-28 | 2008-10-09 | Nippon Paper Chemicals Co Ltd | Additive for bubble-containing composition |
JP5894792B2 (en) * | 2011-12-28 | 2016-03-30 | 花王株式会社 | Solid bath agent |
JP5894790B2 (en) * | 2011-12-28 | 2016-03-30 | 花王株式会社 | Solid bath agent |
JP6031248B2 (en) * | 2012-04-10 | 2016-11-24 | アイカ工業株式会社 | Coating composition |
-
1981
- 1981-08-25 JP JP13372681A patent/JPS5834802A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5834802A (en) | 1983-03-01 |
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